MXPA97004921A - Process for the funcionalization of superfic - Google Patents

Abstract

The present invention describes a novel coating process comprising the use of a functional photoinitiator, or a macroinitiator derived therefrom, in a cascade of process steps, wherein, on the one hand, a functional photoinitiator or a macroinitiator derived therefrom link in a covalent manner with a carrier, and on the other hand, an oligomer or polymer forming a new surface layer is covalently linked to the functional photoinitiator or to the carrier modified by a functional photoinitiator, by means of functional groups which are co-reactive with isocyanate groups. The invention also relates to novel intermediates that are carriers, with which the functional photoinitiators containing isocyanate groups are linked.

Description

PROCESS FOR THE FÜNCIONALIZACION OF SURFACES The present invention relates to a novel coating process comprising the use of a functional photoinitiator, or a macroinitiator derived therefrom, in a cascade of process steps, wherein, on the one hand, a functional photoinitiator or a macroinitiator derived from the same is covalently linked to a carrier, and on the other hand, an oligomer or polymer forming a new surface layer is covalently bound to the functional photoinitiator, or to the carrier modified by a functional photoinitiator, by means of functional groups that are co-functional. reagents with isocyanate group. The invention also relates to novel intermediates which are carriers with which functional photoinitiators containing free isocyanate groups are linked. The superficial modification of polymers has been the focus of interest for many years. The properties of a polymer often have to satisfy different physical and chemical requirements that, due to the material used, can often be satisfied only in part. One possible way to satisfy these requirements is to cover a base material with a thin layer of a second material. The latter must supply the properties that are missing in the first material, but not alter the fundamental properties of the base material. In relation to this, he puts special attention to a better biocompatibility in the broadest sense, for example, to the wettability of polymeric surfaces. A pioneering work in the field of polymer surface modification, which aims to specifically improve the wettability of contact lens surfaces, has come from Yasuda et al., J. Biomed. Mater. Res. 9, 629 (1975). The authors describe a process in which a 20 nanometer thick layer is applied by plasma polymerization of a mixture of acetylene, water, and nitrogen, to a polymethyl methacrylate contact lens. The plasma is produced in an apparatus for the downstream coating, with a discharge of brightness of high frequency, and an operating frequency of 13.56 MHz. The contact angle of an untreated polymethyl methacrylate surface, according to the method of drop of water, is approximately 71 ° and after the plasma polymerization coating just described, approximately 37 °. Another attractive method for applying thin hydrophilic films to substrates is to use unsaturated alcohols in the plasma polymerization. Hozumi et al., Puré & Appl. Chem. 60, 697 (1988), describe a method of discharge of high frequency brightness wherein they employ allyl alcohol and propargyl alcohol, and also 2-methyl-3-butin-2-ol. The tests, carried out mainly with alcohol propargyl, show that a contact angle of 45 ° results after coating. If in addition water is added to the operating gas in the plasma polymerization, contact angle can still be reduced to 20 °. When such a coated product is swelled with water, however, it is found that the additional layer exhibits unsatisfactory adhesion to the substrate. Two more recent publications, PCT-AU 89/00220 and H. J. Griesser, Materials Forum, 14 (1990) 192, deal with a plasma polymerization method where compounds are applied Organic, such as saturated alcohols, saturated amines, derivatives or mixtures thereof, and inorganic gases, such as oxygen, hydrogen, nitrogen, helium, argon, or neon, and water vapor, such as a plasma polymer to a lens contact. According to the authors, the water content should be between a maximum of 20 percent by volume, and preferably 5 percent by volume. It is intended that the presence of water be to prevent excessive crosslinking of the plasma polymer. Examples are given where films are applied by plasma polymerization of ethanol and isobutanol. During the discharge of brightness, the substrates are subjected to an energy of approximately 1 watt / square centimeter between two parallel flat electrodes. If there is a sufficiently high static potential on these substrates, high-energy spontaneous discharges are released which heat the substrate very much and : > •: cause internal tensions. As a result, they are produced plasma polymer deposits that are highly cross-linked and that are difficult to control. The Patent Number WO 94/06485 describes a multilayer material, especially a biomedical article and preferably a contact lens, having one or more wettable surfaces capable of containing an intact film of aqueous fluid, the multilayer material consisting of a base material and a hydrophilic layer, and the hydrophilic layer is formed by a carbohydrate derivative which is covalently linked with reactive groups on the surface of the base material, either directly or indirectly by means of functional groups of an additional oligofunctional compound which extends between the base material and the hydrophilic layer, and is covalently bonded on both sides. By the specific use of suitable functional photoinitiators in a multi-stage coating process, it has now become possible to precisely control the nature of the applied layers by different reaction mechanisms, i.e., photochemical and chemical reaction mechanisms. The use of functional photoinitiators makes it possible to produce tightly bonded surface layers of high uniformity, layer thickness, coating density, and durability. European Patent Number EP-A-632,329 already describes functional photoinitiators which are also used in accordance with the present invention. However, according to this prior art, the photoinitiators are always used in such a way that first the isocyanate group thereof reacts with the co-reactive groups on the surface of the substrate. The union of the oligomers or polymers that form a new surface by means of radicals is then carried out by the part of the photoinitiator. In contrast, the process according to the invention, a different route, wherein, although on the one hand a functional photoinitiator or a macroinitiator derived therefrom is also covalently linked to a carrier, on the other hand the oligomer or polymer forming a new The surface layer is bonded to the carrier modified by a functional photoinitiator by means of groups that are co-reactive with isocyanate groups. Although photoinitiators are also linked to surfaces according to European Patent Number EP-A-632,329, new surfaces on a carrier can be formed in the last step of the process only by ethylenically unsaturated, photopolymerizable, or photocrosslinkable substances. In contrast, the present invention makes it possible, after photochemical functionalization of the surface using functional photoinitiators, to produce a new surface using a number of known prefabricated synthetic oligomers or polymers, or biomaterials carrying H-active groups.

Accordingly, the present invention relates to a novel coating process comprising, on the one hand, covalently binding a functional photoinitiator containing at least one isocyanate group, or a macroinitiator derived therefrom, to a carrier, and another part, to covalently link an oligomer or polymer, forming a new surface layer, with the functional photoinitiator or with the carrier modified by a functional photoinitiator by means of functional groups that are co-reactive with the isocyanate groups. The functional photoinitiator is preferably a compound of the formula Ia or Ib. subsequently, macroinitiators derived therefrom are also described. The process according to the invention preferably applies to the surface of a biomedical article, a textile or industrial molded article, especially to the surface of an ophthalmic molded article, for example a contact lens. As a result of this coating, hydrophilic, water repellent, slippery, colorable, anti-pollution, and biocompatible surfaces are produced, for example, on an inorganic or organic base material. In addition, it is also possible to produce layers that provide the base material with protection against wear, abrasion, corrosion, (photo) oxidation, bioerosion, or undesirable deposits (such as dirt, proteins, lipids, salts, tartar, microorganisms, cosmetics, chemicals, etc.), or that form a barrier against entry, emigration, or the permeation of undesirable substances (gases, liquids, or solids). The present invention relates preferably to a coating process comprising the following steps: (a) applying a thin layer of a functional photoinitiator of the formula Ia or Ib to a surface containing suitable groups that are co-reactive with the radicals; (b) irradiating the coated surface with ultraviolet light of a suitable wavelength, producing, by cleavage of radical a in the functional photoinitiator, radicals in the form of benzoyl which form a covalent bond with the co-reactive groups on the surface, while that the isocyanate groups of the photoinitiators are preserved; (c) applying to the surface modified by a photoinitiator, an oligomer or polymer containing groups that are co-reactive with the isocyanate groups. (d) a covalent bond being formed by the oligomer or polymer with the isocyanate groups of the photoinitiators covalently bonded to the surface. The present invention also preferably relates to a coating process comprising the following steps: (a) reacting an oligomer or polymer containing groups that are co-reactive with the isocyanate groups, with a functional photoinitiator of the formula Ib, to form a macroinitiator, the isocyanate group of the photoinitiator forming a covalent bond with one of the co-reactive groups of the oligomer or polymer; (b) applying a thin layer of the macroinitiator thus obtained, to a surface containing suitable groups that are co-reactive with radicals; (c) irradiating the coated surface with ultraviolet light of a suitable wavelength, producing by radical dissociation a in the macroinitiator, radicals in the form of benzoyl which form a covalent bond with the co-reactive groups on the surface. The present invention preferably relates, in addition, to a coating process comprising the following steps: (a) where applicable, providing to the surface of a base material, functional groups that are co-reactive with isocyanate groups, for example OH, NH2 or COOH, by suitable chemical or physical pretreatment, for example plasma treatment; (b) covering the surface containing groups that are co-reactive with isocyanate groups, with a functional photoinitiator of formula la or Ib, forming a isovalent group of the photoinitiator with a covalent bond with the surface, - (c) covering the modified surface by a photoinitiator, with a thin layer of a vinyl monomer that contains at least one isocyanate group or a mixture of vinyl monomers containing this monomer; (d) irradiating the coated surface with ultraviolet light of a suitable wavelength, producing a graft (co) polymer containing isocyanate groups, which is covalently bound to the surface; (e) applying to the surface so modified, an oligomer or polymer containing groups that are co-reactive with the isocyanate groups; (f) forming a covalent bond by the oligomer or the polymer with the isocyanate groups of (co) graft polymer. The invention also relates to base materials that have been coated according to the invention, especially films or ophthalmic molded articles, for example contact lenses. These also include base materials that have been treated in accordance with the invention, but do not possess the ultimately modified surface, and which, rather, have been treated according to the invention only up to the stage where they still contain free isocyanate groups. These are, for example, base materials that can be obtained according to claim 2, when only steps (a) and (b) described therein are carried out, or when steps (c) and (d) are omitted. described therein, or basic materials that can be obtained according to claim 4, when only the steps (a) to (d) described therein, or when steps (e) and (f) described therein are omitted. Within the scope of the present invention, the term "carrier" means a material that can be either a base material or a final surface material itself, or a suitable intermediate layer. Examples of these carriers are glass, silica gels, ceramics, metal, wood, silicate minerals, metal oxides, and preferably, natural or synthetic oligomers or polymers of all kinds. Natural oligomers and polymers are, for example, oligo- and poly-saccharides or derivatives thereof, peptides, proteins, glycoproteins, enzymes, antibodies, and growth factors. Some examples are cyclodextrins, trehalose, cellobiose, lactose, lactosamine, lactobiono-lactose, maltotriose, maltohexaose, chitohexaose, agarose, chitin 50, amylose, starch, hyaluronic acid, deacetylated hyaluronic acid, chitosan, glucans, heparin, xylan, pectin, galactan , poly-galactosamine, glycosaminoglycans, dextran, aminated dextran, cellulose, hydroxyalkyl cellulose, carboxyalkyl cellulose, fucoidan, chondroitin sulfate, sulfated polysaccharides, mucopolysaccharides, gelatin, zein, collagen, albumin, globulin, bilirubin, ovalbumin, keratin, fibronectin and vitronectin , pepsin, trypsin ^, and lysozyme. The oligomers and synthetic polymers can be, for example, hydrolyzed polymers or polymers of esters or ethers vinyl (polyvinyl alcohol); polydiolefins or hydroxylated polydiolefins, for example, polybutadiene, polyisoprene, or polychloroprene, or copolymers thereof; polyacrylic acid and polymethacrylic acid, and also polyacrylates, polymethacrylates, polyacrylic amides or polymethacrylic amides, if desired to have hydroxyalkyl or aminoalkyl radicals in the ester group or in the amide group; polysiloxanes if desired to have hydroxyalkyl or aminoalkyl groups; aminated polyethers or polyethers of epoxides or glycidyl compounds and diols; polyvinylphenols or copolymers of vinylphenol and olefinic comonomers; and copolymers of at least one monomer from the group of vinyl alcohol, vinyl pyrrolidone, acrylic acid, methacrylic acid, or acrylates containing hydroxyalkyl or aminoalkyl, methacrylate, or acrylic amide or methacrylic amide, or hydroxylated diolefins or diolefins with ethylenically unsaturated comonomers, examples are acrylonitrile, olefins, diolefins, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, styrene, α-methylstyrene, vinyl ethers and vinyl esters; polyoxaalkylenes, if desired to have pendant or terminal OH or aminoalkyloxy groups. The term "vinyl monomer containing at least one isocyanate group" means especially an isocyanate containing one or more lower alkenyl groups, for example, an isocyanato lower alkyl acrylate or methacrylate, or styrene substituted by isocyanate or lower isocyanatoalkyl, or an alkenyl isocyanate or alkenyl isocyanate, for example vinyl isocyanate, allyl isocyanate, or acryloyl isocyanate. By proper choice of a carrier, the properties of a surface, or of a material in general, can be well controlled. For example, a surface can be made hydrophilic or hydrophobic, depending on the required use. Other properties that can be imparted in this manner are, for example, slippage, colorability, anti-pollution properties, or biocompatibility. The functional photoinitiators used according to the invention are compounds of the formula Ia or Ib: OCN - R4 NHC -Y -) -R2 (la), O R 101 OCN-R 5 -NH-C-Y10X -C -C-Ci NR, 03R104 n,) R102 100 where Y is 0, NH or NR] A; Yj is 0; Y2 is -0-, -0- (0) C-, -C (0) -0- or -0-C (0) -0-; each n independently of the other, is 0 or 1; R is H, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms-NH-; R | and 2 are each independently of the other, H, straight or branched alkyl of 1 to 8 carbon atoms, hydroxyalkyl of 1 to 8 carbon atoms, or aryl of 6 to 10 carbon atoms, or two R? (Y? ) n- are together - (CH2) X-, or the groups Rj- (Yj) n- and R2"(??) n" are Junt ° s a radical of the formula: R3 is a straight or branched bond of 1 to 8 straight or branched carbon atoms which is unsubstituted or substituted by -OH and / or optionally interrupted by one or more -O-, -OC (O) - or -0-C groups (0) -0-; R 4 is alkylene of 3 to 18 carbon atoms branched, arylene of 6 to 10 carbon atoms unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms, or aralkylene of 7 to 18 atoms carbon unsubstituted or substituted by alkyl of 1 to 4 carbon atoms 0 by alkoxy of 1 to 4 carbon atoms, cycloalkylene of 3 to 8 carbon atoms unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms, cycloalkylene of 3 to 8 carbon atoms -CyH2y- unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by alkoxy 1 to 4 carbon atoms, or -CyH2y- (cycloalkylene of 3 to 8 carbon atoms) -CyH2y- unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms; R5 independently has the same definitions as R4, or is alkylene of 3 to 18 linear carbon atoms; R1A is lower alkyl; x is an integer from 3 to 5, • y is an integer from 1 to 6; Ra and Rb are each independently of the other, H, alkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, benzyl or phenyl; with the proviso that n in the groups - (Y?) n-R? let 0 be when R2 is H; that no more than two Yi of the groups - (Y?) n- are O and n of the other group - (Y * ¡) n- is 0; and that n in the group - (Y2) n "is 0 when R3 is a direct bond, and where also: X is -O- bivalent, -NH-, -S-, lower alkylene, or Y10 is a direct bond u -0- (CH2) y- where y is an integer from 1 to 6, and whose terminal CH2 group is linked to the adjacent X in formula (Ib); RJOO is H, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, alkyl of 1 to 12 carbon atoms-NH-, or -NR1ARjB where R ^ A is lower alkyl, and R1B is H or lower alkyl; RJQJ is straight or branched lower alkyl, lower alkenyl, or arylalkyl; Rl02 regardless of Rioi »has the same definitions as R? O? > ° is aryl, or R101 R102 are Junt ° s - (CH2) m-, where m is an integer from 2 to 6; R03 and 104 are each independently of the other, linear or branched lower alkyl which may be substituted by alkoxy of 1 to 4 carbon atoms, or arylalkyl or lower alkenyl; or R103 and R104 are together "* -CH2) z"? ll "^ CIÍ2 ^ z" wherein YJJ is a direct bond, -O-, -S- or -NRlB-, and R1B is H or lower alkyl, and each z independently of the other is an integer from 2 to 4. In a preferred embodiment, Y is 0. R1A as alkyl may be, for example, methyl, ethyl, normal propyl or isopropyl, normal butyl, isobutyl, or butyl tertiary, pentyl, or hexyl. R1A is of methyl preference. The group R contains as alkyl, alkoxy, or alkyl-NH-, preferably from 1 to 6, and especially from 1 to 4 carbon atoms. Some examples are methyl, ethyl, normal propyl or isopropyl, normal butyl, isobutyl, or tertiary butyl, pentyl, hexyl, octyl, decyl, dodecyl, methoxy, ethoxy, propoxy, butoxy, and methyl-NH-. More preferably R is H. Rl as alkyl is preferably linear and preferably contains 1 to 4 carbon atoms. Some examples are methyl, ethyl, normal propyl or isopropyl, normal butyl, isopropyl, or tertiary butyl, pentyl, hexyl, heptyl, and octyl. Rj is preferably methyl or ethyl. Rj as aryl may be, for example, naphthyl, or especially phenyl. When the two groups R? - (Y?) N- are together - (CH2) X-, x is preferably 4, and especially 5. R1 as hydroxyalkyl is preferably linear, and preferably contains from 1 to 4 atoms of carbon.

Some examples are hydroxymethyl and 2-hydroxyethyl-1-yl. For R2 the same preferred definitions apply as for Rj. R2 is preferably H, methyl, or ethyl. Ra and b are preferably each independently of the other, H or alkyl of 1 to 4 carbon atoms, for example, methyl or ethyl. In a preferred subgroup, Rj is preferably ethyl and especially methyl, or the two groups R? - (?) N- are together pentamethylene, n in the group - (Y?) nR is preferably 0, R is preferably methyl, hydroxymethyl, or H, and R is H. In another preferred embodiment, in the group - (?) n-R2, Yj is O, n is ly and R2 is H. In this case, n in the groups R? - (?) n-is especially 0. R3 contains as alkylene preferably from 1 to 6, and especially from 1 to 4 carbon atoms , and the alkylene is preferably linear. Some examples are methylene, ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, pentylene, hexylene, heptylene, and octylene. Methylene, ethylene, 1,3-propylene, and 1,4-butylene are preferred. More especially, R3 is ethylene; or a direct bond, in which case n in the group - (Y) n- is 0. When R3 is alkylene substituted by hydroxy, it may be, for example, especially 2-hydroxy-1,3-propylene or also 2-hydroxy -l, 3- or -1,4-butylene. Alkylene interrupted by -0-e unsubstituted or substituted by -OH is, for example, -CH2CH2-0-CH2CH2-, -CH2CH2-O-CH2CH2-0-CH2CH2-, -CH2CH2-0-CH2CH2-0-CH2CH2-O -CH2CH2-, [-CH (CH3) CH2-0-CH (CH3) CH2-], CH (CH3) CH2-0-CH2CH2-, -CH (C2H5) CH2-0-CH2CH2-, [-CH (C2H5 CH2-0-CH (C2H5) CH2-] or CH2CH2CH2CH2-0-CH2CH2CH2CH2- and CH2CH (0H) CH2-0-CH2CH2-. Alkylene interrupted by -0-C (0) - or -C (0) -0- is, for example, -CH2CH2-C (0) -0-CH2- or CH2CH2-0-C (0) -CH2-. Alkylene interrupted by -0-C (0) -0- is, for example, -CH2CH2-0-C (0) -0-CH2CH2- or -CH2CH2-0-C (O) -0-CH2-.

Alkyl substituents of 1 to 4 carbon atoms and alkoxy of 1 to 4 carbon atoms are preferably methyl or ethyl and methoxy or ethoxy. R 4 contains, as branched alkylene, preferably from 3 to 14 and especially from 4 to 10 carbon atoms. Examples of alkylene are 1, 2-propylene, 2-methyl- or 2, 2-dimethyl-1,3-propylene, 1,2-, 1,3-, and 2,3-butylene, 2-methyl- or 2,3-dimethyl-1,4-butylene, 1,2-, 1,3- or 1,4-pentylene, 2-methyl- or 3-methyl- or 4-methyl- or 2,3-dimethyl- or 2,4-dimethyl- or 3,4-dimethyl- or 2,3,4-trimethyl- or 2,2,3-trimethyl- or 2,2,4-trimethyl- or 2,2,3,3-tetramethyl - or 2, 2, 3, 4-tetramethyl-l, 5 -pentylene, 1,2-, 1,3- 1,4- or 1,5-hexylene, 2-methyl- or 3-methyl- or 4- methyl- or 2,2-dimethyl- or 3,3-dimethyl- or 2,3-dimethyl- or 2,4-dimethyl- or 3,4-dimethyl- or 2, 2, 3-trimethyl- or 2, 2 , 4-trimethyl- or 2, 2, 5-trimethyl- or 2,3,4-trimethyl- or 2, 2, 4, 5-tetramethyl-l, 6-hexylene, 1,2-, 1,3-, 1,4-, 1,5- or 1,6-heptylene, 2-methyl- or 3-methyl- or 4-methyl- or 5-methyl- or 2,2-dimethyl- or 3,3-dimethyl- or 2,3-dimethyl- or 2,4-dimethyl- or 3,4-dimethyl- or 2,2,3-trimethyl- or 2,2,4-trimethyl- or 2,2,5-trimethyl- or 2, 2, 6-trimethyl- or 2, 3, 4-trimethyl- or 2,4,5-trimethyl- or 2,4,6-trimethyl- or 2, 2,4,5-tetra amethyl-l, 7-heptylene, 1,2-, 1,3-, 1,4-, 1,5-, 1,6- or 1,7-octylene, 2-methyl- or 3-methyl- or -methyl- or 5-methyl- or 6-methyl- or 7-methyl- or 2,2-dimethyl- or 3,3-dimethyl- or 2,3-dimethyl- or 2,4-dimethyl- or 3, 4 -dimethyl- or 2,6-dimethyl- or 2,7-dimethyl- or 2, 2, 4-trimethyl- or 2, 2, 5-trimethyl- or 2, 2, 6-trimethyl- or 2,2,5 , 6-tetramethyl-l, 8-octylene, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, or 1, 8-nonylene, 2-methyl- or 3-methyl- or 4-methyl- or 5-methyl- or 6-methyl- or 7-methyl- or 8-methyl- or 2,2 -dimethyl- or 3,3-dimethyl- or 2,3-dimethyl- or 2,4-dimethyl- or 3,4-dimethyl- or 2,6-dimethyl- or 2,7-dimethyl- or 2,8- dimethyl- or 2, 2, 4-trimethyl- or 2, 2, 5-trimethyl- or 2, 2, 6-trimethyl- or 2, 2, 7-trimethyl- or 2, 2, 8-trimethyl-nonylene, 1 , 2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, or 1,9-decylene, 2-methyl- or 3-methyl- or 4-methyl- or 5-methyl- or 6-methyl- or 7-methyl- or 8-methyl- or 9-methyl- or 2,2-dimethyl- or 3,3-dimethyl- or 2,3-dimethyl- or 2,4-dimethyl- or 3,4-dimethyl- or 2,6-dimethyl- or 2,7-dimethyl- or 2, 8-dimethyl- or 2,9-dimethyl-1, 10-decylene, 1, 2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, or 1,1,10-undecylene, 2-methyl- or 3-methyl- or 4-methyl- or 5-methyl- or 6-methyl- or 7-methyl- or 8-methyl- or 9-methyl- or 10-methyl-1, 11-undecylene, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, or 1,11-dodecylene. Some preferred branched alkylene radicals are 2,2-dimethyl-1,4-butylene, 2,2-dimethyl-1,5-pentylene, 2,2,3-or 2,2,4-trimethyl-1., 5-pentylene, 2, 2-dimethyl-l, 6-hexylene, 2,2,3- or 2,2,4- or 2, 2, 5-trimethyl-1,6-hexylene, 2,2-dimethyl -l, 7-heptylene, 2,2,3- or 2,2,4- or 2,2,5- or 2, 2,6-trimethyl-l, 7-heptylene, 2,2-dimethyl-1, 8-octylene, 2,2,3- or 2,2,4- or 2,2,5- or 2,2,6-, or 2,2,7-trimethyl-l, 8-octylene. When R 4 is arylene, it is preferably naphthylene, and especially phenylene. When the eirylene is substituted, a substituent is preferably in the ortho position with respect to an isocyanate group. Examples of substituted arylene are 1- methyl, 2,4-phenylene, 1,5-dimethyl-2"4-phenylene, l-methoxy-2,4-phenylene, and l-methyl-2,7-naphthylene. R 4 as aralkylene is preferably naphthylalkylene, and especially phenylalkylene. The alkylene group in the aralkylene preferably contains from 1 to 12, more preferably from 1 to 6, and especially from 1 to 4 carbon atoms. More preferably, the alkylene group in the aralkylene is methylene or ethylene. Some examples are 1,3-, or 1,4-benzylene, naphth-2-yl-7-methylene, 6-methyl-l, 3- or 1,4-benzylene, 6-methoxy-1,3- or 1 , 4-benzylene. When R 4 is cycloalkylene, cyclopentylene of 5 or 6 carbon atoms is preferably unsubstituted or substituted by methyl. Examples are 1, 3-cyclobutylene, 1,3-cyclopentylene, 1,3- or 1,4-cyclohexylene, 1,3- or 1,4-cycloheptylene, 1,3-, or 1,4-, or 1 , 5-cyclooctylene, 4-methyl-l, 3-cyclopentylene, 4-methyl-l, 3-cyclohexylene, 4, 4-dimethyl-l, 3-cyclohexylene, 3-methyl- or 3, 3-dimethyl-l, 4-cyclohexylene, 3,5-dimethyl-1,3-cyclohexylene, 2,4-dimethyl-1,4-cyclohexylene. When R4 is cycloalkylene-CyH2y-, it is preferably cyclopentylene-CyHy-, and especially cyclohexylene -CyH2y- which is unsubstituted or preferably substituted by 1 to 3 alkyl groups of 1 to 4 carbon atoms, especially methyl groups. In the group -CyHy-, and is preferably an integer from 1 to 4. More preferably, the -CyH2y- group is ethylene and especially methylene. Some examples are cyclopent-1-yl-3-methylene, 3-methyl-cyclopent-1-yl-3-methylene, 3"4-dimethyl-cyclopent-1-yl-3-methylene, 3,4,4-trimethyl. -cyclopent-1-yl-3-methylene, cyclohex-1-yl-3- or -4-methylene, 3- or 4- or 5-methyl-cyclohex-l-yl-3- or -4-methylene, 3 , 4- or 3, 5-dimethyl-cyclohex-l-yl-3- or -4-methylene, 3,4,5- or 3,4,4- or 3, 5, 5-trimethyl-cyclohex-l- il-3- or -4-methylene. When R4 is -CyH2y-cycloalkylene-CyHy-, it is preferably -CyHy-cyclopentylene-CyH2y-, and especially -CyHy-cyclohexylene-CyH2y- which is unsubstituted or preferably substituted by 1 to 3 alkyl groups of 1 to 4 atoms of carbon, especially methyl groups. In the group -CyH2y-, and is preferably an integer from 1 to 4. More preferably, the groups -CyH2y- are ethylene, and especially methylene. Some examples are cyclopentan-1,3-dimethylene, 3-methyl-cyclopentan-1,3-dimethylene, 3,4-dimethyl-cyclopentan-1,3-dimethylene, 3,4,4-trimethyl-cyclopentane-1,3. -dimethylene, cyclohexan-1, 3- or 1,4-dimethylene, 3- or 4- or 5-methyl-cyclohexan-1, 3- or 1,4-dimethylene, 3,4- or 3,5-dimethyl- cyclohexan-1, 3- or -1,4-dimethylene, or 3,4,5- or 3,4,4- or 3,5,5,5-trimethyl-cyclohexane-1,3- or 1,4-dimethylene. When R5 has the same definitions as R4, the preferred definitions given hereinabove for R4 also apply. R5 contains as linear alkylene preferably from 3 to 12, and especially from 3 to 8 carbon atoms. Some examples of linear alkylene are 1,3-propylene, 1,4-butylene, 1, 5-pentylene, 1,6-hexylene-, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,1-undecylene, 1 , 12-dodecylene, 1, 14-tetradecylene, and 1,18-octadecylene. A preferred definition of X is -0-, -NH-, -S- or lower alkylene. More preferably, X is -0- or -S-, and especially -O-. In a preferred definition of Y ^, the subscript y is from 1 to 5, more preferably from 2 to 4, and more preferably 2 or 3, such that Y10 is, for example, ethyleneoxy or propyleneoxy. In another preferred definition, Y10 is a direct bond, with X preferably being, or containing at least one heteroatom. The group R10o contains as alkyl, alkoxy, alkyl-NH- or -NRjAR? B, preferably from 1 to 6 and especially from 1 to 4 carbon atoms. Some examples are methyl, ethyl, normal propyl or isopropyl, normal butyl, isobutyl or tertiary butyl, pentyl, hexyl, octyl, decyl, dodecyl, methoxy, ethoxy, propoxy, butoxy, N, N-dimethylamino, and N-methylamino. More preferably R is H. A preferred definition of -NR1AR1B is N, N-dimethylamino, N-methylamino, N-methyl-N-ethylamino, N-ethylamino, N, N-diethylamino, N-isopropylamino, or N, N- diisopropylamino. RjOi is preferably allyl, benzyl or alkyl of 1 to 4 linear carbon atoms, for example methyl or ethyl. Rlo has preferably the same definitions as RJQJ, and is more preferably linear lower alkyl having from 1 to 4 carbon atoms, and especially 1 or 2 carbon atoms. RIQ2 as aryl may be, for example, naphthyl, or especially phenyl which is unsubstituted or substituted by lower alkyl or lower alkoxy. When R ^ gi and R102 are together - (CH2) m-, m is preferably 4 or 5, and especially 5. R103 is preferably linear lower alkyl having from 1 to 4 carbon atoms, benzyl or allyl, and more preferably methyl or ethyl. R104 is preferably linear lower alkyl having from 1 to 4 carbon atoms, and more preferably methyl or ethyl. When Rj03 and R104 are together - (CH2) Z-Yjj- (CH2) Z, Yn is preferably a direct bond, -O-, or -NIC ^) -, and more preferably -0-; 2 is preferably 2 or 3, and especially 2. A preferred subgroup of compounds of the formula comprises those wherein: in the groups Rj (Yj) n-, n is 0, Y, Y2, and Yj in the group R2 - (Y1) n-, are each O, n in the group R2"(Y?) N" is ° ° l? Rj is alkyl of 1 to 4 carbon atoms or phenyl, or the groups R? ~ (Y?) N "are together tetramethylene or pentamethylene, R is alkyl of 1 to 4 carbon atoms or H, R is hydrogen, n in the group - (Y 2) n- is 0 or 1, and R 3 is alkylene of 2 to 4 straight or branched carbon atoms, or is a direct bond, in which case, n in the group - ( Y2) a- is 0, R4 is alkylene of 5 to 10 branched carbon atoms, phenylene, or phenylene substituted with 1 to 3 methyl, benzylene or benzylene groups substituted with 1 to 3 methyl, cyclohexylene or cyclohexylene groups substituted by 1 to 3 methyl groups, cyclohexyl-CyH2y- or - (l ^ H ^ -cyclohexyl-CyH ^ - or cyclohexyl-CyH2y- or -CyH2y-cyclohexyl-CyH2y- substituted by 1 to 3 methyl groups, R5 has the same definitions that R4, or is alkylene of 3 to 10 linear carbon atoms, and y is 1 or 2. An especially preferred subgroup of compounds of the formula comprises those wherein: in the groups R * ¡- (Y?) n- and "(Y2) n" 'p is 0, Y, Y2, and Yj in the group R2- (Y?) N "are each O, n in the group R2- (Y?) N- is 0 or 1, Rj is methyl or phenyl, or the groups? - (Y?) N "are together pentamethylene, R2 is methyl or H, R is hydrogen, n in the group - (Y) n- is 1, and R3 is ethylene, or n in the group - (Y2) n- is 0 and R3 is a direct bond, R4 is alkylene of 6 to 10 branched carbon atoms, phenylene or phenylene substituted by from 1 to 3 methyl groups, benzylene or benzylene substituted by from 1 to 3 methyl groups, cyclohexylene or cyclohexylene substituted by from 1 to 3 methyl groups, cyclohexyl-CH2- or cyclohexyl-CH2- substituted by from 1 to 3 methyl groups, R 5 has the same definitions as R 4, or is alkylene of 5 to 10 linear carbon atoms. A preferred subgroup of compounds of the formula Ib comprises those wherein: RjOi is linear lower alkyl, lower alkenyl, or arylalkyl lower; R102 independently of Rioi "has the same definitions as RJOI" is aryl, • R103 and R104 are each independently of the other, linear or branched lower alkyl which may be substituted by alkoxy of 1 to 4 carbon atoms, or arylalkyl or lower alkenyl; or Rj03 and R104 are together - (CH2) Z-Y11- (CH2) Z-, wherein YJJ is a direct bond, -O-, -S- or -NR1B-, and R1B is H or alkyl lower, and each z independently of the other is an integer from 2 to 4; and R 5 is linear or branched 3 to 18 carbon atoms, arylene of 6 to 10 carbon atoms unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, aralkylene of 7 to 18 carbon atoms unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms, arylenenalkylenearylene of 13 to 24 carbon atoms unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms, cycloalkylene of 3 to 8 carbon atoms unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, cycloalkylene of 3 to 8 carbon atoms-CyH2y- unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms, or -CyH2y- (cycloalkylene of 3 to 8 carbon atoms) - CyH2y-unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms, where y is an integer of 1 to 6. A preferred subgroup of compounds of the formula Ib comprises those wherein: X is -O- bivalent, -NH-, -S- or - (CH2) and-; YjO is a direct link u -0- (CH2) y- where y is an integer from 1 to 6, and whose terminal CH2 group is linked to the X adjacent in the formula (Ib); RgOO is H, alkyl of 1 to 12 carbon atoms, or alkoxy of 1 to 12; RjOi is linear lower alkyl, lower alkenyl, or arylalkyl lower, - Rj ^ independently of R10j has the same definitions as RJQI Ó is aryl, or R101 R102 are Jun os - (CH2) m "in d * onde m is an integer of 2 to 6, Rj03 and 104 are each independently of the other, straight or branched lower alkyl which may be substituted by alkoxy of 1 to 4 carbon atoms, or arylalkyl or lower alkenyl, or R103 and R104 are together - (CH2) Z-Yn- (CH2) Z- where Yn is a direct bond, -O-, -S- or -NR1B-, and R1B is H or lower alkyl, and each z independently of the other is an integer from 2 to 4 , - and R 5 is branched C 6 to C 10 alkylene, phenylene or phenylene substituted with 1 to 3 methyl, benzylene or benzylene groups substituted with 1 to 3 methyl groups, cyclohexylene or cyclohexylene substituted with 1 to 3 methyl groups , cyclohexylene-CH2- or cyclohexylene-CH2- substituted by from 1 to 3 methyl groups, an especially preferred subgroup of of the Formula Ib comprises those wherein: R10j is methyl, allyl, toluylmethyl or benzyl, R10 is methyl, ethyl, benzyl, or phenyl, or RjOi and RJO2 are together pentamethylene, Rj03 and R104 are each independently of the other, lower alkyl having up to 4 carbon atoms, or R103 and R104 are together -CH2CH2OCH2CH2-, and R5 is alkylene of 6 to 10 branched carbon atoms, phenylene or substituted phenylene of 1 to 3 methyl groups, benzylene or benzylene substituted by 1 to 3 groups methyl, cyclohexylene or cyclohexylene substituted by 1 to 3 methyl groups, cyclohexylene-CH2- or cyclohexylene-CH2- substituted by from 1 to 3 methyl groups. The groups R4 and R5 are especially groups in which the radioactivity of the OCN group is reduced, this being achieved essentially by steric hindrance or by electronic influences on at least 1 adjacent carbon atoms. R4 and R5, therefore, are preferably alkylene which is branched at position a, or especially at the position β with respect to the group OCN, or are cyclic hydrocarbon radicals which are substituted as defined in at least one position a. Some examples of especially preferred compounds are: OCNCH2C (CH3) 2CH2CH (CH3) (CH2) 2NHC (0) 0 (CH2) 20 -V- C (0 > OC CH H3) 2N-mortblinyl NH-C (0) -0- (CH2) 2-0-pC6H4-C (0) -C (CH3) 2-N-? Norpholinyl The preparation of a compound of the formula Ia or Ib comprises reacting a compound of the formula Ilia or IIb: where X, Y, Yj, Y2, Q, R, R R2, R3, RJOO R02 Ri02-R103 'R104 and n are as defined hereinbefore, preferably in an inert organic solvent, with a diisocyanate of the Illa or Illb formula, or with an optionally mono-masked diisocyanate, OC-R4-NCO (Illa), OCN-R5-NCO (IHb) where R and R5 are as defined above at the moment. Preferred examples of diisocyanates in which the reactivity of the two isocyanate groups is distinctly different are, for example, hexane-1,6-diisocyanate, 2,2,4-trimethylhexan-1,6-diisocyanate, 1,3-bis- (3-isocyanatopropyl) -tetramethyldisiloxane, tetramethylene diisocyanate, phenylene-1,4-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, m- or p-xylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate , 1, 5 - naph t il endi i soc aiana, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylsulfondiisocyanate, or 4,4'-dicyclohexylmethanediisocyanate. Masking agents are known from urethane chemistry. It may be, for example, phenols (cresol, xyleneol), lactams (e-caprolactam), oximes (acetoxime, benzophenone oxime), methylene-H-active compounds (diethyl malonate, ethyl acetoacetate), pyrazoles or benzotriazoles. The masking agents are described, for example, by Z.W. icks, Jr. in Progress in Organic Coatings, 9 (1981), pages 3-28. Starting materials of the type shown in formula Ia or Ilb are known and described, for example in European Patent Numbers EP-A-284, 561,-EP-A-117, 233, or EP-A-088,050. Suitable inert solvents are aprotic, preferably polar, solvents, such as, for example, hydrocarbons (petroleum ether, methylcyclohexane, benzene, toluene, xylene), halogenated hydrocarbons (chloroform, methylene chloride, trichloroethane, tetrachloroethane, chlorobenzene), ethers (diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, glycol dimethyl ether) of diethylene, tetrahydrofuran (THF), dioxane), ketones (acetone, dibutyl ketone, methyl isobutyl ketone), carboxylic acid esters and lactones (ethyl acetate, butyrolactone, valerolactone), alkylated carboxylic acid amides (N, N-dimethyl acetamide) , N, N-dimethyl formamide (DMF) or N-methyl 2-pyrrolidone (NMP)), nitriles (acetonitrile), sulfones and sulfoxides (dimethyl sulfoxide (DMSO), tetramethylene sulfone). Preferably, polar solvents are used. The reagents are conveniently used in equimolar amounts. The reaction temperature can be, for example, from 0 ° C to 200 ° C. When catalysts are used, the temperatures can conveniently be in the range of -20 ° C to 60 ° C, and preferably in the range of -10 ° C to 50 ° C. Suitable catalysts are, for example, metal salts, such as alkali metal salts, carboxylic acids, tertiary amines, for example (alkyl of 1 to 6 carbon atoms) (triethyl amine, normal tributyl amine), N-methyl pyrrolidine, N-methyl morpholine, N, N-dimethyl piperidine, pyridine, and 1,4-diaza-bicyclooctane. It has been discovered that some tin compounds are especially effective, especially the alkyl tin salts of carboxylic acids, such as, for example, dibutyltin dilaurate, or, for example, tin dioctoate. If free OH or NH groups are present in the compounds of the formula Ia or Ib, these groups can initially be protected by suitable protecting groups during the reaction with a diisocyanate, and subsequently can be released again by removing the protecting groups. Suitable protecting groups are known to the person skilled in the art. Representative examples can be found, for example in T.W. Greene, "Protective Groups in Organic Synthesis", Wiley Interscience, 1981, The isolation and purification of the prepared compounds, are carried out according to known methods, for example extraction methods, crystallization, recrystallization, or chromatographic purification. The compounds are obtained in high yields and purities. The yields in the case of non-optimized processes can be more than 85 percent of the theoretical yields. The term "macroinitiator" is used within the scope of the present invention to mean an oligomer or polymer having one or more -OH and / or -NH-, H-active groups, linked in a terminal or pendant manner, if wishes by means of one or more bridging groups, the H atoms of whose H-active groups are partially or completely substituted by radicals - > or?' wherein R2oo is a radical of the formula IVa or IVb: O O v_v II (Y,) nR? -C (0) HN R4 NHC - Y - R3 - (Y2) -? - C - C - (Y,) - R n ^ -f l p (IVa), R (Y?) - R? O O R, 01 -C (O) NH-R5-NH- C-Y10 X ('^ C-C NR103R104 (rVb) R 102 where X, Y, Y Y2, Y10, R, R R2, R3, R4, R5, RJOO RIOP R102 'R103' R104 and n are as defined hereinabove. The H-active groups are preferably -COOH, OH- or -NH- groups. The oligomers may have, for example, an average molecular weight of 300 to 10,000 Daltons, and preferably contain at least 3, more preferably from 3 to 50, and especially from 5 to 20 structural units. As is known, the transition between the oligomers and the polymers is fluid and can not be exactly defined. The polymers may contain from 50 to 10,000, more preferably from 50 to 5,000 structural units, and may have an average molecular weight of 10,000 to 1,000,000, preferably 10,000 to 500,000. The oligomers and polymers can also comprise up to 95 mole percent, preferably 5 to 90 mole percent of comonomeric structural units without H-active groups, based on the polymer. The oligomers and polymers having H-active groups can be natural or synthetic oligomers or polymers. The examples of these have already been mentioned previously. Preferred oligomers and polymers are, for example, cyclodextrins having a total of 6 to 8 ring-forming glucose structural units, or hydroxyalkyl or aminoalkyl derivatives, or derivatives further substituted by glucose or maltose radicals, of which at least a structural unit corresponds to the formula (V): wherein R7, Rg, and Rn are each independently of the others, H, alkyl of 1 to 4 carbon atoms, especially methyl, acyl of 2 to 6 carbon atoms, especially acetyl, hydroxyalkyl of 1 to 4 carbon atoms , especially hydroxymethyl or 2-hydroxyethyl-l, aminoalkyl of 2 to 10 carbon atoms and especially aminoalkyl of 2 to 4 carbon atoms, for example 2-aminoet-1-yl or 3-aminoprop-1-yl or 4 -aminobut-1-ilo, X! is -0- or -NRjB- wherein, per cyclodextrin unit, a total of 1 to 10, and preferably 1 to 6 radicals Xj can be -NR1B-, and the remaining radicals Xj are -O-, wherein RjB is hydrogen or lower alkyl, - and at least one of the radicals R7, Rg, and R9, is a radical of the formula (VI): -R10-R200 < VI > wherein the variables are as previously defined herein, and R10 is a direct bond, (alkylene of 1 to 6 carbon atoms-O-) or - (alkylene of 2 to 10 carbon atoms-NH) -. In a preferred embodiment, from at least half of the glucose units to 6 to 8 glucose units contain at least one radical of the formula (VI). Also preferred is an embodiment wherein only one glucose unit carries a radical of the formula (VI). For X, Y, Yj, Y2 'Y10' R 'R1' R2 'R3' R4 'R5' R100 'R101' R102 'R103' R104 and n 'the preferred definitions given hereinabove apply. RJQ is preferably a direct bond -CH2-0-, -CH2CH2-0-, -CH2CH2-NH-, -CH2CH2CH2-NH- or -CH2CH2CH2CH2CH2-NH-. Preferred oligomers or polymers are especially biomolecules, for example hyaluronic acid, dextran or collagen. Other preferred oligomers and polymers are, for example, oligo- and polysiloxanes having OH or NH2 groups on the alkyl, alkoxyalkyl, or aminoalkyl end groups, or on the side chains, whose H atoms are substituted by a photoinitiator according to the invention. They can also be random, alternating, or segmented copolymers or oligomers, for example block copolymers. The most preferred oligomers and polymers are those comprising: a) from 5 to 100 molar percent of structural units of the formula (VII): b) from 95 to 0 mole percent of structural units of the formula (VIII): based on the oligomer or polymer, wherein RJJ is alkyl of 1 to 4 carbon atoms, lower alkenyl, lower cyanoalkyl, or aryl, each unsubstituted or partially or completely substituted by F, and preferably is methyl, ethyl, vinyl, allyl, phenyl, cyanopropyl, or trifiuoromethyl, -R12 is alkylene of 2 to 6 carbon atoms, preferably 1,3-propylene, or alkylene interrupted once or several times by -0- or -NH-, for example - (CH2) z- (0-CH2-CHCH3-) z-, or (CH2) z- (0-CH2-CH2) Z-, preferably, for example, - (CH2) 3- (0- CH2-CHCH3-) 2-, wherein each z independently of the other is an integer from 2 to 4; Rj4 has the same definitions as Rjj, or is -R12-X, -H or -RJ2 ~ XJ-R15-H; Xj is -0- or -NH-, and R13 is a radical of the formula (IX): -R15"R200 (IX) wherein the variables have the definitions given hereinabove, including their preferred definitions, and R15 is a direct bond or a group -C (0) - (CHOH) r -CH2-0-, where r is 0 or a whole from 1 to 4. Xj is preferably -NH-. The oligomers or polymers described above contain one or more pendant radicals of the formula IX, or in addition to one or more pendant radicals of the formula IX, also one or two terminal radicals of the formula IX. The preferred oligomeric and polymeric siloxanes are also those of the formula (X): wherein Rlt is alkyl of 1 to 4 carbon atoms, vinyl, allyl, or phenyl, each unsubstituted or partially or completely substituted by F, and is preferably methyl, - R 12 is alkylene of 2 to 6 carbon atoms, 1,3-propylene preference; Rj4 has the same definitions as RJJ, or is R? 2-Xj-H or -R12-X1-R15-H, X] is -0- or -NH-; s is an integer from 0 to 1000, and preferably from 0 to 100; and R13 is a radical of formula (IX) above, wherein the variables have the definitions given hereinbefore, including the preferred definitions, and R15 is a direct bond or a group -C (O) - (CHOH) r - CH2-0-, where r is 0 or an integer from 1 to 4. X] is preferably -NH-. Other preferred oligomers and polymers are those based on oligovinyl and polyvinyl alcohol, wherein the H atoms in the OH groups are partially or completely substituted by a radical of the formula (VI). They can be homopolymers with structural units of -CH2CH (0H) -, or copolymers with other monovalent or bivalent olefin structural units. Oligomers and polymers comprising: a) from 5 to 100 molar percent of structural units of the formula (XI): and b) from 95 to 0 mole percent of structural units of the formula (XII): wherein R16 is a radical of formula (VI) above, wherein the variables have the definitions given hereinbefore, including the preferred definitions, and RJ is a direct bond, - (alkylene of 1 to 4 carbon atoms) O) - or - (alkylene of 2 to 10 carbon atoms-NH) -; R17 is H, alkyl of 1 to 6 carbon atoms, -COOR20 or -COO " , - Rjg is H, F, Cl, CN, or alkyl of 1 to 6 carbon atoms, - and R) 9 is H, OH, RIQ-H, F, Cl, CN, R2o- '- alkyl of 1 to 12 carbon atoms, -COO ", -COOR20, -OCO-R20, methylphenyl, or phenyl, wherein R? Q is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, 1 to 12 carbon atoms) -cycloalkyl of 5 to 7 carbon atoms, phenyl, (alkyl of 1 to 12 carbon atoms) -phenyl, benzyl or (alkyl of 1 to 12 carbon atoms) benzyl. R17 is preferably H. When R17 is alkyl, it is preferably methyl or ethyl. When R17 is -COOR20, R2n is preferably alkyl of 1 to 12 carbon atoms, especially alkyl of 1 to 6 carbon atoms. When Rj is alkyl, it is preferably alkyl of 1 to 4 carbon atoms, for example methyl, ethyl, normal propyl, or normal butyl. R18 is preferably H, Cl, or alkyl of 1 to 4 carbon atoms. When R19 is the group R20-O-, R20 is preferably alkyl of 1 to 12 carbon atoms, especially alkyl of 1 to 6 carbon atoms. When R19 is alkyl, it preferably contains from 1 to 6, especially from 1 to 4, carbon atoms. When R19 is the group -COOR20, R2Q is preferably alkyl of 1 to 12 carbon atoms, especially alkyl of 1 to 6 carbon atoms, or cyclopentyl or cyclohexyl. When R19 is the group -OCO-R20, R2Q is preferably alkyl of 1 to 12 carbon atoms, especially alkyl of 1 to 6 carbon atoms, or phenyl or benzyl. In a preferred embodiment, R17 is H, R18 is H, F, Cl, methyl, or ethyl, and R19 is H, OH, F, Cl, CN, alkyl of 1 to 4 carbon atoms, alkoxy of the 6 carbon atoms. carbon, hydroxyalkoxy of 1 to 6 carbon atoms, -COO-alkyl of 1 to 6 carbon atoms, -OOC-alkyl of 1 to 6 carbon atoms, or phenyl. Oligomers and polymers in which R17 is H, Rj8 is H or methyl, and R19 is H, OH, CN, methyl, OCH3, 0 (CH2) tOH or -C00CH3, and t is an integer from 2 to 6 are especially preferred. Another preferred group of oligomers and polymers comprises oligo- or poly-acrylates or -methacrylates, or partially or fully hydroxyalkylated -acrylamides or -methacrylamides, wherein the hydroxy group or the primary amino group, respectively, is substituted by a radical of the formula (IX) above. They may comprise, for example, from 5 to 100 mole percent of structural units of the formula (XIII): and from 95 to 0 mole percent of structural units of the formula (XIV): where R2 (is H or methyl; X2 and X3 are each independently of the other, -0-, or -NH-; R22 is (CH2) C- and e is an integer from 2 to 12, preferably from 2 to 6; R23 is a radical of the formula (IX); Rj7 and Rjg are as previously defined herein; and R24 has the same definitions as R19, or is -C (0) X2R22X3H. For R23, R17, R18, and R19, the preferred definitions mentioned hereinbefore apply. For X2 and? 3, the preferred definitions mentioned hereinbefore apply. Other preferred oligomers and polymers are those consisting of polyalkylene oxides, wherein the H atoms of the terminal OH or -NH2 group are partially or completely substituted by radicals of the formula (IX). They can be, for example, those of the formula (XV) having identical or different structural repeating units - [CH2CH (R26) -0] - R25 [(CH2CH-0-). -R27-x4-R28 (XV) R26 wherein: R25 is the group R28-X4-, or is the v-valent radical of an alcohol or polyol having from 1 to 20 carbon atoms, R26 is H, alkyl of 1 to 8 carbon atoms, preferably alkyl from 1 to 4 carbon atoms, and especially methyl, R27 together with X4 is a direct bond, or R27 is alkylene of 2 to 6 carbon atoms, preferably alkylene of 3 to 6 carbon atoms, and especially 1,3-propylene, X is -0-, or -NH- , R2 is a radical of the formula (IX), each or independently of the other, is a numerical value from 3 to 10,000, preferably from 5 to 5000, especially from 5 to 1000, and more especially from 5 to 100, and v is an integer from 1 to 6, preferably from 1 to 4. R 25 can be a mono- to tetra-valent radical of an alcohol or polyol. When R 2 is the radical of an alcohol, R 5 is preferably alkyl or alkenyl of 3 to 20 straight or branched carbon atoms, cycloalkyl of 3 to 8 carbon atoms and especially 5 to 6 carbon atoms, -CH- ( cycloalkyl to 6 carbon atoms), aryl of 6 to 10 carbon atoms, and especially phenyl and naphthyl, aralkyl of 7 to 16 carbon atoms and especially benzyl and l-phenyleth-2-yl. The cyclic or aromatic radicals can be substituted by alkyl of 1 to 18 carbon atoms or alkoxy of 1 to 18 carbon atoms. When R25 is the radical of a diol, R25 is preferably alkylene or alkenylene of 3 to 20 branched and especially linear carbon atoms, and more preferably alkylene of 3 to 12 carbon atoms, cycloalkylene of 3 to 8. carbon atoms and especially from 5 to 6 carbon atoms, -CH2- (cycloalkyl of 5 to 6 carbon atoms) -, -CH2- (cycloalkyl of 5 to 6 carbon atoms) -CH2-, aralkylene of 7 to 16 carbon atoms, and especially benzylene, -CH2- (aryl of 6 to 10 carbon atoms) -CH2- and especially xylylene. The cyclic or aromatic radicals can be substituted by alkyl of 1 to 12 carbon atoms or by alkoxy of 1 to 12 carbon atoms. When R25 is a trivalent radical, it is derived from aliphatic or aromatic triols. R 25 is preferably a trivalent aliphatic radical having from 3 to 12 carbon atoms, which is derived especially from triols having preferably primary hydroxy groups. More preferably, R25 is -CH2 (CH-) CH2-, HC (CH2-) 3 or CH3C (CH2-) 3. When R25 is a tetravalent radical, it is preferably derived from aliphatic tetroles. R25 in this case is preferably C (CH2-). Preferably, R25 is a radical derived from Jeffamins (Texaco), a Pluriol, a Poloxamer (BASF) or poly (tetramethylene oxide). For R28, the preferred definitions mentioned hereinabove apply. Particularly preferred are homo-oligomers and homo-polymers and block oligomers and block polymers, each having structural units of the formula - [CH2CH2-0] or [CH2CH (CH3) -O] - Also suitable are the fluorinated polyethers corresponding to formula (XVI):R25 [(CF2CF-0-) u] v R27- X4- R2g (XVI), wherein: R27, R2, X, u and v are as defined hereinabove, R25 is as defined hereinabove, or is the monovalent radical of a partially fluorinated or perfluorinated alcohol having from 1 to 20, preferably from 1 to 12, and especially of 1 to 6 carbon atoms, or the bivalent radical of a partially fluorinated or perfluorinated diol having from 2 to 6, preferably from 2 to 4, and especially 2 or 3 carbon atoms, and Rd is F or perfluoroalkyl having from 1 to 12, preferably from 1 to 6, and especially from 1 to 4 carbon atoms. R < j is especially -CF3. Other suitable oligomers and polymers are, for example, polyamines, such as polyvinyl amine, or polyethylene imines, wherein the H atoms of the NH groups are substituted by a radical of the formula (VI), including the aforementioned preferences. The poly-e- is also suitable lysine The oligomers and polymers according to the invention can be prepared simply and in a manner known per se, by reacting a compound of the formula Ia or Ib with oligomers and functional polymers of HO or NH. Within the scope of the present invention, hereinafter and hereinafter, and unless otherwise reported, arylene is preferably phenylene or naphthylene, each unsubstituted or substituted by lower alkyl or by lower alkoxy, especially 1 , 3-phenylene, 1,4-phenylene, or methyl-1,4-phenylene, or 1,5-naphthylene or 1,8-naphthylene. Within the scope of the present invention, aryl has up to 24, and preferably up to 18 carbon atoms, and is a carbocyclic aromatic compound that is unsubstituted or substituted by lower alkyl or by lower alkoxy. Examples are phenyl, toluyl, xylyl, methoxyphenyl, tertiary butoxy-phenyl, naphthyl, or phenanthryl. Within the scope of this invention, unless otherwise defined, the term "lower" used in connection with radicals and compounds, especially denotes radicals or compounds having up to 8 carbon atoms, preferably up to 6 carbon atoms. carbon. Lower alkyl has especially up to 8 carbon atoms, preferably up to 6 carbon atoms, and is, for example, example, methyl, ethyl, propyl, butyl, tertiary butyl, pentyl, hexyl, or isohexyl. Lower alkenyl is linear or branched alkenyl having from 2 to 8 carbon atoms, preferably from 2 to 6 carbon atoms, and especially from 2 to 4 carbon atoms. Examples of alkenyl are vinyl, allyl, l-propen-2-yl, 1-buten-2- or -3- or -4-yl, 2-buten-3-yl, and the isomers of pentenyl, hexenyl, or octenyl. Unless defined otherwise, alkylene has up to 10 carbon atoms, and can be straight or branched chain. Suitable examples include decylene, octylene, hexylene, pentylene, butylene, propylene, ethylene, methylene, 2-propylene, 2-butylene, or 3-pentylene. Alkylene is preferably lower alkylene. Lower alkylene is alkylene having up to 8, and especially up to 6 carbon atoms. An especially preferred definition of lower alkylene is methylene or ethylene. The arylene alkylene or arylene alkylene unit is preferably phenylene which is unsubstituted or substituted by lower alkyl or by lower alkoxy; the alkylene unit thereof is preferably lower alkylene, such as methylene or ethylene, especially methylene. Preferably, therefore, these radicals are phenylenemethylene or methylenephenylene.

Lower alkoxy has especially up to 8 carbon atoms, preferably up to 6 carbon atoms, and is, for example, methoxy, ethoxy, propoxy, butoxy, tertiary butoxy, or hexyloxy. Within the scope of the present invention, arylalkyl lower has up to 30, preferably up to 24, and especially up to 18 carbon atoms, and is lower alkyl substituted by aryl. Examples of arylalkyl lower are benzyl, xylylmethyl, toluylethyl, phenylbutyl, tertiary butoxy-phenylmethyl, naphthylpropyl, methoxyphenylmethyl, or phenylhexyl. The photochemical stimulus of a photoinitiator, or polymerization, is carried out with known methods, for example, by irradiation with light which is high with short-wave radiation, and is preferably ultraviolet light. Suitable light sources are, for example, medium pressure, high pressure, and low pressure mercury radiators, super-actinic fluorescent tubes, metal halide lamps, or laser devices, whose maximum emission is on the scale of 250 to 450 nanometers. In the case of a combination with photosensitizers or ferrocene derivatives, it is also possible to use beams of light or laser of a longer wavelength of up to 600 nanometers. In certain cases, it may be convenient to use mixtures of 2 or more of the aforementioned photoinitiators. Of course, you can also use mixtures with customary commercial photoinitiators, for example mixtures with benzophenone, acetophenone derivatives, benzoin ethers, or benzyl ketals. To accelerate a photochemical step, amines can be added, for example trietanolic amine, N-methyl-dietanolic amine, p-dimethylaminobenzoic acid ethyl ester, or Michler's ketone. The action of the amines can be enhanced by the addition of aromatic ketones of the benzophenone type. Acceleration can also be caused by the addition of photosensitizers, which change or extend the spectral sensitivity. These are especially aromatic carbonyl compounds, for example derivatives of benzophenone, thioxanthone, anthraquinone, and 3-acylcoumarin, and 3- (aroylmethylene) -thiazolines. If desired, the photochemical reaction step can be specifically sensitized at certain wavelength scales of the light, and thus, when several photoinitiators are being used, the sequence of the reaction can be controlled in a specific manner. The effectiveness of a photoinitiator used can be increased by the addition of titanocene derivatives having fluoro-organic radicals, as described in European Patent Numbers EP-A-122,223 and EP-A-186,626, for example in an amount of 1. to 20 percent. Examples of these titanocenes are bis (methylcyclopentadienyl) -bis (2,3,6-trifluorophenyl) -titanium, bis (cyclopentadienyl) -bis (4 - dibutylamino-2, 3, 5, 6-tetrafluorophenyl) -titanium, bis (methylcyclopentadienyl) -2- (trifluoromethyl) phenyl-titanium isocyanate, bis (cyclopentadienyl) -2- (trifluoromethyl) -phenyl-titanium trifluoroacetate, or bis (methylcyclopentadienyl) -bis (4-decyloxy-2,3,5,6-tetrafluorophenyl) -titanium. The liquid a-amino ketones are especially suitable for these mixtures. In the process for coating a surface, in addition to a photoinitiator, different additives may be used, usually in small amounts. Examples of the latter are thermal inhibitors, which are intended, for example, to prevent premature polymerization, such as, for example, hydroquinone or sterically hindered phenols. In order to increase storage stability in the dark, it is possible to use, for example, copper compounds, phosphorus compounds, quaternary ammonium compounds, or hydroxyl amine derivatives. For the purpose of excluding atmospheric oxygen during copolymerization, paraffin or similar waxy substances may be added that migrate to the surface when the polymerization begins. As light-protecting agents, it is possible to add, in small amounts, ultraviolet absorbers, for example those of the benzotriazole, benzophenone, or oxalanilide type. It is still better to add light-protective agents that do not absorb ultraviolet light, such as, for example, sterically hindered amines (HALS).

The examples given below serve to illustrate the present invention in greater detail, however, they are not intended to limit its scope in any way. Unless otherwise reported, temperatures are given in degrees Celsius.

Preparation Examples Example To 2-dimethylamino-2-benzyl-1- (4- (2-hydroxyethoxy) phenyl) -butan-1-one.

The title compound is prepared according to the synthesis described in European Patent Number EP-A-284, 561.

B-jompIn A2 2-ethyl-2-dimethylamino-1- (4- (2-hydroxyethoxy) phenyl) -pent-4-en-l-one.

The title compound is prepared in a quantitative yield in a manner analogous to Example A. Yellowish crystals remain in a m.p. of 80-82 ° C.

Eiemolo A3 2 -ethyl-2-dimethylamino-1- (4- (2-hydroxyethoxy) phenyl) -pentan-1-one. 32. 6 grams (0.11 moles) of 2-ethyl-2-dimethylamino-1- (4- (2-hydroxyethoxy) phenyl) -pent-4-en-l-one according to Example A2, are dissolved in 220 milliliters of ethyl acetate, - 1.6 grams of palladium on carbon (5 percent) are added thereto, and then the mixture is hydrogenated at 30 ° C under normal pressure. After about 3 hours, the hydrogen portion ceases (2.58 liters, 103 percent of the theoretical amount). The catalyst is removed by filtration, and the solvent is distilled using a rotary evaporator (RE). The oily residue is purified by evaporation chromatography (petroleum ether / ethyl acetate 2: 1). 27.4 grams (84 percent) of a slightly yellowish oil remain.

Example A4 1- (4- (2-Hydroxythioethyl) phenyl) -2-methyl-2-morpholino-propan-1-one.

The preparation of the title compound is described in European Patent Number EP-A-088,050.

P ompl n A 5 1- (4- (2-Hydroxyethoxy) phenyl) -2-methyl-2-morpholino-propan-1-one, The title compound is prepared in a manner analogous to Example A4.

E! J «wrnpl r > Afi Preparation of the following compound: In a 100-milliliter flask equipped with reflux condenser, thermometer, stirrer, and nitrogen inlet tube, 2.92 grams (10 mmol) of 2-ethyl-2-dimethylamino-1- (4- (2-hydroxyethoxy) are dissolved. phenyl) -pent-4-en-l-one (from Example A2) in 30 milliliters of dry methylene chloride, and the solution is mixed with 2.22 grams (10 millimoles) of isophorone diisocyanate in 30 milliliters of dry methylene chloride . 2.0 milligrams of dibutyltin dilaurate catalyst is added thereto, and stirring is carried out at room temperature for 72 hours. The course of the reaction is monitored by thin layer chromatography (the eluent is toluene / acetone 6: 1). Then the reaction solution is stirred in water. The organic phase is separated and washed twice more with water. The organic phase is dried over MgSO4 and concentrated using a rotary evaporator. The remaining residue is purified by column chromatography (toluene / acetone 6: 1). 3.4 grams (66 percent) of a yellow oil remain. The structure is verified by proton nuclear magnetic resonance, infrared and elemental analysis.

Example A7 In a manner analogous to Example A6, the following isocyanate is prepared from 1.17 grams (4 millimoles) of 1- (4- (2-hydroxyethoxy) phenyl) -2-methyl-2-morpholino-propan-1- ona (from Example A5), and 0.7 grams (4 millimoles) of 2,4-toluene diisocyanate using dibutyl tin dilaurate as a catalyst in methylene chloride. After the addition of 50 milliliters of ether and 200 milliliters of petroleum ether to the reaction mixture, the objective compound is precipitated in a crystalline form. It is filtered, washed with petroleum ether, and then dried under vacuum to give the compound shown below, of a m.p. of 97-l02 ° C.

Ti! J «» mp1 na A8. A9, and A10 In a manner analogous to Example A6, the following compounds are prepared: , where R is one of the following radicals: OR Example No. A8 R = O -O- JL N Example No. A9 R = Example No. A10 R = TT-j < - »tn 1r > All In a manner analogous to Example A6, the following compound is prepared: Example Al2 In a manner analogous to Example A6, the following isocyanate is prepared from 5.1 grams (29.3 millimoles) of 2, 4-toluene diisocyanate (TDI) and 10 grams (29.3 mmol) of 2-dimethylamino-2-benzyl-1- (4- (2-hydroxyethoxy) phenyl) -butan-1-one (from Example Al), using dilaurate of dibutyl tin like catalyst- in methylene chloride. The reaction mixture is diluted with 500 milliliters of diethyl ether and 2 liters of petroleum ether, upon which the product is precipitated. It is filtered, washed with diethyl ether / petroleum ether, and dried under vacuum. A beige powder having a softening scale of 99-103 ° C is obtained.

Example A13: Preparation of NH-C (0) -0-CH2CH2-0-p-C6H4-C (0) -C (CH3) 2-OH In a 500-milliliter flask equipped with a reflux condenser, thermometer, stirrer, and nitrogen inlet tube, a solution of 11,125 grams (0.05 moles) of isophorone diisocyanate (IPDI) freshly distilled in 50 milliliters of dry methylene chloride, is mixed under nitrogen with a solution of 11.2 grams (0.05 moles) of 4 '- (jS-hydroxyethoxy) -2-hydroxyprop-2-yl-phenone (Darocure 2959R) in 300 milliliters of methylene chloride dry, and after the addition of 20 milligrams of dibutyl tin dilaurate as catalyst, the reaction mixture is stirred at room temperature for 48 hours. The course of the reaction is monitored by means of thin layer chromatography on silica gel plates (60 F254 >; Art. 5719 Merck) (eluent: toluene / acetonitrile 7: 3). The resulting product is released from the small amounts of unreacted Darocure 2959 and di-substituted isophorone diisocyanate by column chromatography on silica gel 60 (eluent of toluene / acetonitrile 7: 3). After concentration of the pure fractions by evaporation using a rotary evaporator, a colorless oil is obtained which, upon cooling to -16 ° C, crystallizes slowly, and then recrystallized from dry diethyl ether. 15.6 grams of a white crystalline product (70 percent of theory) are obtained which has a melting point of 76 ° C. The isocyanate content of the product is determined by titration with dibutyl amine in toluene: calculated: 2242 m Val / g, found. 2.25 m Val / g. The method is described in "Analytical Chemistry of Polyurethanes "(High Polymer Series XVI / part III, editors D.S. David &H.B. Staley, Interscience Publishers, New York 1969, page 86). you-«ampi A14; Preparation of: OCNCH2C (CH3) 2CH2CH (CH3) (CH2) 2NHC (0) 0 (CH2) 2? - Y- C (0) C (CH3) OH In a manner analogous to Example A13, 10.5 grams (0.05 moles) of 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI) are reacted with 11.1 grams (0.05 miles) of Darocure 2959R in 400 milliliters of sodium chloride. dry methylene for 40 hours at room temperature under nitrogen 14.5 grams (67 percent of theory) of a white crystalline product with a melting point of 41-43 ° C are obtained. NCO titration: calculated 2.30 m Val / g. found: 2.36 m Val / g.

Example A15: Preparation of: In the apparatus described in Example A13, 1.74 grams (0.01 moles) 2,4-toluene diisocyanate (TDI) are reacted in 20 milliliters of dichloromethane, with 2.24 grams (0.01 moles) of Darocure 2959® dissolved in 60 milliliters of dry dichloromethane. Without the addition of a catalyst, the reaction mixture is stirred at room temperature for 48 hours, and at 40 ° C for 1 hour, until Darocure can no longer be detected 2959 unreacted in a thin layer chromatogram. The product is isolated by precipitation of the reaction solution in 180 milliliters of dry petroleum ether (bp 40-60 ° C), and then recrystallized twice from dichloromethane / petroleum ether, 1 :3. A white crystalline product having a melting point of 124-125 ° C is obtained. Yield of 17.2 grams, which corresponds to 87 percent of the theory. Titration with OCN: calculated: 2.50 m Val / g, found 2.39 m Val / g.

Bl Preparation of macro-initiators Example Bl Preparation of an oligomeric photoinitiator: where R = and x: y is extremely and n is 5 0. 7 grams (1.3 mmol) of the isocyanate of Example A6, 20 milliliters of dry methylene chloride, and 2.55 grams (0.51 m Val NH2 / g) of aminoalkylpolysiloxane KF 8003 (Shin Etsu, Japan), are placed in an apparatus according to with Example A6. The reaction mixture is stirred at room temperature for 2 hours, and at 40 ° C for 20 minutes. The solvent is then removed using a rotary evaporator. The residue is released from the solvent residues under a high vacuum (40 ° C, 0.001 mbar (0.1 Pa)). The title compound is obtained in a quantitative yield. In the infrared spectrum, there is no OCN band.

Example B2 In a manner analogous to Example Bl, an oligomeric photoinitiator having the structure according to Example Bl, is prepared from 0.76 grams (1.3 mmol) of the isocyanate of Example A10, and 2.55 grams (0.51 m Val NH2 / g) of aminoalkylpolysiloxane KF 8003 (Shin Etsu, Japan), where R has the following definition: Example B3 In a manner analogous to Example Bl, an oligomeric photoinitiator having the following structure is prepared, starting from 0.55 grams (0.97 mmol) of the isocyanate of Example A9, and 1.47 grams (0.7 m Val NH2 / g) of aminoalkyl polysiloxane X -22-161B (Shin Etsu, Japan): wherein x is about 38, and R corresponds to the radical of the title compound of Example A9 minus the isocyanate.

Example B4 In a manner analogous to Example Bl, a solution of 1.0 grams (1.95 millimoles) of the isocyanate of Example A6 in 20 milliliters of dry acetonitrile is mixed with 2.24 grams (0.84 m Val NH2 / g) of Jeffamin ED 2001 (Texaco , USA) in 30 milliliters of dry acetonitrile, and the mixture is stirred at room temperature for 24 hours. After work, 3.2 grams (99 percent) of the following photoinitiator are obtained: R-NHCONH-CHCH3CH2- (OCHCH3CH2) a- (OCH2CH2) b- (OCHCH3CH2)? -NHC0NH-R wherein a + c = 2.5 and b = 40.5, and R corresponds to the radical of the title compound of Example A6 minus the isocyanate.

Example B5 In an apparatus according to Example A6, 1.65 grams of polyvinyl alcohol (PVA) (ServaR 03/20, molecular weight of approximately 13,000), are dissolved at 80 ° C under nitrogen, in 2-pyrrolidone N-methyl. The solution is then cooled to room temperature, and a solution of 1.0 gram (1.88 millimoles) of the isocyanate of Example A8 in 10 milliliters of 2-pyrrolidone N-methyl, and 5 milligrams of dibutyl tin dilaurate is added thereto as catalyst. This mixture is then heated at 40 ° C for 48 hours. After that time, OCN can not be detected by infrared analysis at 2,250 cm "1. The reaction mixture is cooled to room temperature, and 700 milliliters of diethyl ether are added thereto, precipitating the product. of the washing with diethyl ether, and then drying under a high vacuum, there remain 1.9 grams of a white product that, according to the elemental analysis, comprises 2.20 percent of S. Proton nuclear magnetic resonance is consistent with the following structure: - t (CH2-CHOH) a- (CH2-CH0C0NHR) b] n- where n is approximately 10, and a: b = 20: 1; and R corresponds to the radical of the title compound of Example A8 minus the isocyanate.

Bj «ampios B6, B7. and B8 In a manner analogous to Example B5, two polydimethylsiloxanes substituted by hydroxyalkyl (KF-6002 / KF-6001) and a dextran, are reacted with the isocyanate of the Example A8. The following parameters describe these compounds. The yields are approximately 90 percent in all cases. The sulfur content of these compounds is determined by combustion analysis (last column of the Table). Isocyanate of OH-macró ßro Solvent Content Example A8 of S (%) Calculated / Found 0. 5 grams KF-6002, Shin-Etsu, JP Tetrahydrofuran (0.94 millimoles) 1.5 g (0.63 Val OH / g) 1.50 / 1.38 0. 5 grams KF-6001, Shin-Etsu, JP Tetrahydrofuran (0.94 millimoles) 0.85 g (1.1 m Val OH / g) 2.22 / 2.08 0. 5 grams Dextran 8, Serva G (0.94 millimoles) 2.3 g, Molecular Weight of Sulfoxide of approximately 8 to 12,000 dimethyl 1.08 / 0.99 Example B9 In a manner analogous to Example B5, 3.23 grams of collagen (Serva 17440, molecular weight of about 80,000) are dissolved in dimethyl sulfoxide over the course of 12 hours, and then 1.0 grams (1.9 millimoles) of the isocyanate of Example A9 in 10 milliliters of dimethyl sulfoxide. After stirring the reaction mixture at room temperature for 72 hours, it is diluted with 500 milliliters of methanol, upon which the product is precipitated. The product is filtered and washed repeatedly with dry tetrahydrofuran. It is then dried under a high vacuum (0.1 Pa, room temperature, 72 hours). There remain 2.8 grams of a yellow-white product, whose infrared spectrum and proton nuclear magnetic resonance are consistent with the expected structure. ^ l-tlPIC1 * »B10; Preparation of a polydimethylsiloxane containing three pendant groups of the formula shown below: In a flask as described in Example A13, with a capacity of 250 milliliters, a solution of 1 gram of the compound according to Example A13 (0.00224 mol) in 50 milliliters of dry dichloromethane is reacted with 4.37 grams of aminoalkylpolysiloxane (0.515 m Val NH2 / g, Petrarch PS 813R: Mn ~ 3000) dissolved in 100 milliliters of dry dichloromethane. The reaction mixture is stirred at room temperature for 10 hours, and then heated at 40 ° C for 1 hour. After cooling, the solvent is removed by concentration by evaporation using a rotary evaporator. A highly viscous, colorless oil is obtained which is finally released from the traces of the solvent under a high vacuum at 40 ° C and at 10"torr Yield of 5.34 grams, which corresponds to 99.5 percent of the theory.The product no longer exhibits a OCN band in the infrared spectrum.

^ "** ™ T 3 B11-B15 In an analogous manner to Example B10, other amino-functional macromers are reacted with the compound described in Example A13. The results are summarized in Table 3: Table 3: Example Amino Macromer- Structure Compound Yield% N functional according to the (product) (calculated / Example A13 found) BU X-22-161C (Shin Etsu, 1.5 grams 92 grams 1.52 / 1.42 JP) 7.8 g (0.43 m (3.36 mmoles) (99.6%) Val NH2 / g) M ~ 4600 B12 Jeffamin T 403 2.84 grams 5.62 grams 7.08 / 7.11 (Texaco, USA) (6.36 millimoles) (99.7%) 2.8 g (6.38 m Val NH2 / g) B13 JeffaminR D2000 1.786 grams 5.78 grams 2.90 / 2.89 (Texaco, USA) (2.0 millimoles) (99.9%) 4.0 g (1 m Val NH2 / g) B14 KF-8003 1.0 grams 4.55 grams 1.63 / 1.58 (Shin Etsu, JP) (2.29 millimoles) (98.9%) 4.6 g (0.49 m Val NH2 / g) B15 X-22-161B (Shin Etsu, 1.0 grams 4.2 grams 2.23 / 2.09 JP) 3.23 g (0.699 m (2.29 mmoles) (99.3%) Val NH2 / g) M ~ 2900 a = Z - NH- (CH2) 3- NH- Z CH3 I (O- CH2- CH) - - NH - Z / b = H3C - CH2 C - (OCH2 - CH) - NH - Z CH, \ x + y + z - 5-6 (0_CH2 - CH) _ NH_ z CH, = Z NH CH CH 2 - ((CH, CH-) NH- Z 33 CH, CH, NH- C Example B16: Preparation of a: b ~ 30: 1 n ~ 10 In the apparatus described in Example A13, 2.1 grams of polyvinyl alcohol (PVA) (ServaR 03/20 Mn ~ 13,000) are dissolved at 90 ° C under nitrogen in 50 milliliters of 2- N-methyl pyrrolidone (NMP). The solution is cooled to room temperature, and filtered through a G4 glass frit. Then a solution of 0.7 grams (1567 millimoles) of compound according to Example A13 in 10 milliliters of dry N-methyl 2-pyrrolidone is added thereto. After the addition of 10 milligrams of dibutyl tin dilaurate, the reaction mixture is stirred at 50 ° C for 48 hours. After that reaction time, no further unreacted isocyanate can be detected by infrared spectroscopy (OCN at 2280 cm "1) After cooling to room temperature, the product is precipitated in • 400 milliliters of dry diethyl ether, filtered, washed with dry diethyl ether, and dried in vacuo. 2.6 grams of a white product containing 1.38 percent nitrogen are obtained. Chemical changes - JH of aromatic protons of the photoinitiators that are linked with polyvinyl alcohol: d7.00-7-10 (d, 2H); d 8.15-8.25 (d, 2H).

Example B17: Reaction of hyaluronic acid with the reactive photoinitiator according to Example A13. In a manner analogous to Example B16, 444 milligrams of hyaluronic acid (Denki Kagaku Kogyo, Mn-1.2 x 106) dissolved in 100 milliliters of dry dimethyl sulfoxide (DMSO), are reacted at 50 ° C with a solution of 200 milligrams of the compound described in Example A13 in 10 milliliters of dry dimethyl sulfoxide. You get 534 milligrams (82.7 percent of theory) of a white product that carries in about 30 percent of the sugar residues of the polymer backbone, a photoinitiator group bonded as a urethane or as a carboxylic acid amide , as shown by the evaluation of the? -RMN spectrum. Chemical changes of H of aromatic protons of the photoinitiators that bind with hyaluronic acid: d 7.00-7.10 (d, 2H); d 8.15-8.25 (d, 2H).

Examples B18-B20 In a manner analogous to Example B17, the reactive photoinitiator described in Example A13 is reacted with a number of hydroxyalkyl-substituted polydimethylsiloxanes in dichloromethane as a solvent. The results are given in the Table Table 4: Example of photoinitiator Polysiloxane Performance Analysis according to Elemental% Example 1 Calculated / found B18 1.0 grams KF-6002 4.55 grams C 39.87 / 39.86 (2.25 millimoles) (Shin Etsu, JP) (98.9%) H 7.96 / 8.29 3.6 g (0.625 m N 1.36 / 1.04 Val OH / g) B19 1.0 grams F-6001 3.0 grams C 23.49 / 24.11 (2.23 millimoles) (Shin Etsu, JP) (98.3%) H 3.12 / 8.54 2.05 g (1.1 m N 2.03 / 1.79 Val OH / g) B20 1.0 4.8 grams C - / 36.18 (2.25 millimoles) (86.5%) H - / 8.08 Copolymer of N - / l.03 gluconamidopropylmethylmethylsiloxane, 4.55 grams (6,495 m Val OH / g) CH3 CH3 product B18 = Z - Q (CH2) 3- SHO-Si) - (CH2) 3- CH, CH, CH CH product B19 = Z - O (CH2) 3- SHO - Si) - (CH2) 3- I I - CH ^ CHn product B20 = Example B21: Cyclodextrin macroinitiator Cyclodextrins are cyclic oligosaccharides of the formula: wherein n is a number from 6 to 8. It is commercially available, and also hydroxyalkylated derivatives having a degree of substitution of 0.6 to 1.6 per unit of dextrin. The reaction with the photoinitiators according to the invention, generally produces mixtures that include derivatives that have substitution patterns of different types and different degrees of substitution. The preferred position for substitution is the primary hydroxyl group. The mixtures can be separated by chromatography, with mono-substituted derivatives being easily separated into 6 to 8 photoinitiators. In a 250-milliliter amber glass flask equipped with a reflux condenser, stirrer, internal thermometer and dropping funnel, dissolve 5 grams (4.4053 millimoles) of dry ß-cyclodextrin and 0.094 grams of dibutyl tin dilaurate under dry nitrogen in 50 milliliters of dry dimethyl sulfoxide. To this solution is added dropwise, at room temperature, a solution of 13.77 grams (3084 millimoles) of a compound according to Example A13 in 50 milliliters of dry dimethyl sulfoxide. The mixture is stirred first at room temperature for 3 hours, and then at 50 ° C for 15.5 hours. Subsequently, no further unreacted β-cyclodextrin can be detected by chromatography. The reaction mixture is cooled, and the product is precipitated by the addition of 1000 milliliters of dry diethyl ether. The isolated viscous product is dissolved in 25 milliliters of acetone, and again precipitated with 500 milliliters of diethyl ether, producing a white suspension. The product is filtered, and the white powder obtained is washed twice with 100 milliliters of diethyl ether, and then dried under vacuum with the exclusion of light. You get 13.04 grams (53.5 percent of theory) of the product. The nitrogen content of 3.73 percent corresponds to a degree of substitution- average of 5.6 per ring of cyclodextrin. The product is fractionated by evaporation chromatography (column 60 cm in length, and 5 centimeters in diameter) on silica gel (Merck 60 F, particle size 0.04 to 0.063 millimeters) using methanol / toluene (2: 8) as eluent. With 13 grams of the crude product, the following fractions are obtained, with fraction 2 being eluted with methanol only, and fraction 3 with methanol / water (1: 1): fraction quantity (a) content of N (%) average replacement plow 1 1.3 4.25 6.4 2 3.59 3.59 5.4 3 1.36 1.36 2.0 The Production of Polymeric Films and Contact Lenses B-jampIn Cl 5 grams of polybutadiene- (1, 2-syndiotactic) (PB) of Polysciences Inc. (Catalog No. 16317, molecular weight of approximately 10,000) are dissolved at 40 ° C in 100 milliliters of tetrahydrofuran. The solution is then cooled to room temperature, and poured onto a Folanorm sheet (Folex®, Zürich, Switzerland) to produce a film of a solution of polybutadiene- (1,2-syndiotactic) approximately 0.5 millimeters thick. The tetrahydrofuran is slowly evaporated at room temperature under nitrogen. The remaining polybutadiene film is then extracted with ethanol, and dried until its weight is constant.

Example C2 2.2 grams of polybutadiene- (1,2-syndiotactic) are dissolved in 50 milliliters of methylcyclohexane at 40 ° C under nitrogen. A solution of 2 grams of H-siloxane (Experimental Product K-3272, Goldschmidt, Germany) in 5 milliliters of methylcyclohexane is added thereto, and the stirring is carried out for 5 minutes. This solution is then gassed with nitrogen for 30 minutes. Then 3 drops of the platinum divinyltetramethyldisiloxane catalyst are added to this solution (ABCR, PC 072) dissolved in one milliliter of methylcyclohexane, and then the mixture is heated at 50 ° C, with stirring, for 3 minutes. This mixture is then placed between two glass plates to produce a liquid film of approximately 1.5 millimeters thick. This sandwich system is then heated to 60 ° C under nitrogen for 16 hours. Then it is cooled to room temperature, the glass plates are removed, and the polybutadiene film crosslinked with tetrahydrofuran is extracted. After extraction, the crosslinked polybutadiene film is dried until its weight is constant.

Example C3 5.35 grams (1 millimole) of vinyl-containing polysiloxane (Silopren U Additiv V 200, Bayer Leverkusen, Germany) are mixed with 1.13 grams (2 millimoles) of H-siloxane (Experimental Product 1085, Goldschmidt, Germany), and the The mixture is stirred at room temperature under reduced pressure (200 mbar (20kPa)) for 1 hour. Then nitrogen is bubbled through the mixture for 30 minutes, 2 drops of platinum divinyltetramethyldisiloxane catalyst (ABCR, PC 072) are added, and the mixture is stirred for 5 minutes. Then fill polypropylene molds (Ciba Vision Atlanta, suitable for the production of a molded article that has a thickness of 0.5 millimeters and a diameter of 1 centimeter) with this mixture, they are closed and heated in an oven at 60 ° C under nitrogen for 16 hours. The molds are allowed to cool to room temperature, and are opened, and the discs thus produced, which contain crosslinked polyvinylsiloxane, are extracted with ethanol, and subsequently dried until their weight is constant.

B? < »Tnp1 r > C4 Contact lenses consisting of the crosslinked polyvinylsiloxane are produced in a manner analogous to Example C3, using polypropylene molds suitable for the production of soft contact lenses with a thickness of 100 microns, a diameter of 1.4 centimeters, and a base curve of 8.4 millimeters • g owpl ft C5 2.63 grams (0.5 millimoles) of vinyl-containing polysiloxane (Silopren U Additiv V 200) and 3.0 grams of H-siloxane (Experimental Product K 3272), Goldschmidt, Germany) are mixed and stirred at room temperature under reduced pressure (200 mbar (20kPa)) for 1 hour. Then nitrogen is bubbled through the mixture for 30 minutes, two drops of the platinum divinyltetramethyldisiloxane catalyst (ABCR, PC 072) are added, and the mixture is stirred for 10 minutes. Then, polypropylene contact lens molds (Ciba Vision Atlanta, USA) are filled with this mixture, closed and heated in a 60 ° C oven under nitrogen for 16 hours. The molds are allowed to cool to room temperature, and are opened, and the contact lenses thus produced, which contain cross-linked polyvinylsiloxane, are extracted with ethanol, and subsequently dried until their weight is constant.

Example DI 4 grams of the photoinitiator of Example A6 are dissolved under nitrogen in 10 milliliters of acetone. A portion of this solution is sprayed onto a polybutadiene film according to Example Cl, such that, after the acetone has evaporated while being flooded with nitrogen, a uniform photoinitiator film is produced on the polybutadiene film. . Then the coated polybutadiene film it is irradiated with ultraviolet light (12 mW / cm2) for 10 minutes.

The film is subsequently washed three times with acetone, in order to remove the unlinked photoinitiator. Then the film is dried under reduced pressure (0.001 bar (0.1 Pa)) until its weight is constant. The infrared Fourier transform (FT-IR) spectrum of the film exhibits an OCN band at 2,250 cm "1. Finally, the film is immersed for 2 hours in a 5 percent solution of Jeffamin M 2070 in acetone, and then it is completely washed twice with acetone and three times with deionized water.The polybutadiene film thus coated is analyzed in the infrared Fourier transformation spectrum, and then the contact angles are determined (K 12, Krüss GmbH, Hamburg, Germany). polybutadiene film Cl contact angle in [°] advance recoil uncoated 102 78 coated 66 47 Example D2 In a manner analogous to Example DI, a crosslinked polybutadiene film of Example C2 is coated.

Polybutadiene film C2 contact angle in [°] advance recoil uncoated 111 71 coated 96 59 Example D3 In a manner analogous to Example DI, a polybutadiene film of Example Cl is coated with the photoinitiator of Example A8. polybutadiene film Cl contact angle in [°] advance recoil uncoated 102 78 coated 62 46 te1 ?? wr'1 or D4 In a manner analogous to Example DI, the lenses of Example C4 are coated with the photoinitiator of Example A8. polyvinylsiloxane C4 contact angle in [°] advance recoil uncoated 111 78 coated 98 34 • g-j oTn l ri n In a manner analogous to Example DI, a crosslinked polyvinylsiloxane disk of Example C3 is coated with the photoinitiator of Example A6.

C3 disc contact angle in [°] advance recoil uncoated 112 72 coated 99 38 R-j "ampl D6 In a manner analogous to Example DI, a polybutadiene film according to Example Cl is coated with the photoinitiator of Example A6. However, in contrast to Example DI, this film is then immersed in a solution of dimethyl sulfoxide comprising 1 percent Dextran 8 (Serva), and about 1 milligram dibutyl tin dilaurate as a catalyst. polybutadiene film Cl contact angle in [°] advance recoil uncoated 102 78 coated 98 51 Example D7 In a manner analogous to Example DI, a polybutadiene film according to Example Cl is coated with the photoinitiator of Example A6. However, in contrast to Example DI, this film is then immersed in an aqueous solution comprising 5 percent polyethyleneimine (Fluka). polybutadiene film Cl contact angle in [°] advance recoil uncoated 102 78 coated 66 18 B-j t-nripI n Pfl In a manner analogous to Example DI, the contact lenses according to Example C5, is coated with the photoinitiator of Example A6. However, in contrast to the Example DI, these lenses are then immersed in an aqueous solution comprising 5 percent polyethylenimine (Fluka).

C5 contact lenses contact angle in [°] advance recoil uncoated 115 80 coated 99 56 • B? iam l n The 2 grams of macro-initiator according to Example B5, are dissolved in 50 milliliters of dry dimethyl sulfoxide. Nitrogen is bubbled through this solution for 30 minutes. Then a polybutadiene film of Example Cl (2 x 2 centimeters) is immersed in this solution for 10 minutes, and then it is removed and irradiated with ultraviolet light (12 mW / cm2) for 10 minutes. The film thus coated is washed once with dimethyl sulfoxide, twice with isopropanol, once with 50 percent aqueous isopropanol, and once with water. Then the film is dried and analyzed (the thickness of the layer of the hydrophilic film is about 6 microns, determined by means of an optical microscope and Ru04 contrast). polybutadiene of Cl contact angle in [°] advance recoil uncoated 102 78 coated 48 37 B-jo-mplo R2 In a manner analogous to Example El, a cross-linked polybutadiene film of Example C2 is treated with the macro-initiator of Example B5. polybutadiene of C2 contact angle in [°] advance recoil uncoated 111 71 coated 97 38 Example E3 In a manner analogous to Example El, siloxane discs of Example C3 are treated with the macro-initiator of Example B8. siloxane discs of the C3 contact angle in [°] advance recoil uncoated 112 72 coated 94 36 Example E4 In a manner analogous to Example El, contact lenses of Example C4 are treated with the macro-initiator of Example B5. contact lenses of C4 contact angle in [°] advance recoil uncoated 111 78 coated 88 37 g-j.wr.pl E5 In a manner analogous to Example El, contact lenses of Example C5 are treated with the macro-initiator of Example B8.

Contact lenses of the C5 contact angle in [°] advance recoil uncoated 115 70 coated 76 41

Claims (21)

NOVELTY OF THE INVENTION Having described the above invention, it is considered as a novelty, and therefore, the content of the following is claimed as property: CLAIMS

1. A process for multistage coating a surface, which comprises, on the one hand, covalently binding a functional photoinitiator containing at least one isocyanate group, or a macroinitiator derived therefrom, to a carrier, and, for another part, to covalently link an oligomer or polymer, which forms a new surface layer, with the functional photoinitiator or with the carrier modified by a functional photoinitiator, by means of functional groups that are co-reactive with isocyanate groups.

2. A process according to claim 1, which comprises the following steps: (a) applying a thin layer of a functional photoinitiator of the formula Ia or Ib to a surface containing suitable groups that are co-reactive with the radicals , - (b) irradiate the surface covered with ultraviolet light of a suitable wavelength, taking place, by means of radical dissociation in the functional photoinitiator, benzoyl radicals that form a covalent bond with the co-reactive groups on the surface, while the isocyanate groups of the photoinitiators are retained; (c) applying to the surface modified by a photoinitiator, an oligomer or polymer containing groups that are co-reactive with the isocyanate groups. (d) a covalent bond being formed by the oligomer or polymer with the isocyanate groups of the photoinitiators covalently bonded to the surface.

3. A process according to claim 1, which comprises the following steps: (a) reacting an oligomer or polymer containing groups that are co-reactive with the isocyanate groups, with a functional photoinitiator of the formula Ia or Ib , to form a macroinitiator, the isocyanate group of the photoinitiator forming a covalent bond with one of the co-reactive groups of the oligomer or polymer, - (b) applying a thin layer of the macroinitiator thus obtained, to a surface containing suitable groups that are co-reactive with radicals, - (c) irradiate the coated surface with ultraviolet light of a suitable wavelength, producing by dissociation of radical a in the macroinitiator, radicals in the form of benzoyl that form a covalent bond with the co-reactive groups Of the surface.

4. A process according to claim 1, which comprises the following steps: (a) where applicable, providing to the surface of a base material, functional groups that are co-reactive with isocyanate groups, for example OH, NH2 or COOH, by suitable chemical or physical pretreatment, for example plasma treatment; (b) covering the surface containing groups that are co-reactive with isocyanate groups, with a functional photoinitiator of the formula la or Ib, the isocyanate group of the photoinitiator forming a covalent bond with the surface; (c) covering the surface modified by a photoinitiator, with a thin layer of a vinyl monomer containing at least one isocyanate group or a mixture of vinyl monomers containing this monomer; (d) irradiate the coated surface with ultraviolet light of a suitable wavelength, producing a (co) graft polymer containing isocyanate groups, which is covalently bound to the surface; (e) applying to the surface so modified, an oligomer or polymer containing groups that are co-reactive with the isocyanate groups; (f) forming a covalent bond by the oligomer or the polymer with the isocyanate groups of (co) graft polymer.

5. A process according to any one of claims 1 to 4, wherein a compound of the formula Ia or Ib is used as the functional photoinitiator: OR OCN _ R4_NHC -) - 2 (the), OCN- R5- NH- NR 103R104 (Ib) wherein Y is 0, NH or NR1A; Yj is 0; Y2 is -0-, -0- (0) C-, -C (0) -0- OR -0-C (0) -0-; each n independently of the other, is 0 or l; R is H, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms-NH-; Rj and R2 are each independently of the other, H, linear or branched alkyl of 1 to 8 carbon atoms, hydroxyalkyl of 1 to 8 carbon atoms, or aryl of 6 to 10 carbon atoms, or two groups? (Y? ) n- are together - (CH2) X-, or the groups R? - (Yj) n- and R2 ~ (??) n "are together a radical of the formula: / -CH, R3 is a straight or branched linkage of 1 to 8 straight or branched carbon atoms which is unsubstituted or substituted by -OH and / or optionally interrupted by one or more -O-, -OC (O) -O-OC (O) groups ) -O-; R 4 is alkylene of 3 to 18 carbon atoms branched, arylene of 6 to 10 carbon atoms unsubstituted or substituted by alkyl of 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms, or aralkylene of 7 to 18 carbon atoms carbon unsubstituted or substituted by alkyl of 1 to 4 carbon atoms 0 by alkoxy of 1 to 4 carbon atoms, cycloalkylene of 3 to 8 carbon atoms unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms, cycloalkylene of 3 to 8 carbon atoms -CyH2y- unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by alkoxy 1 to 4 carbon atoms, or -CyH2y- (cycloalkylene of 3 to 8 carbon atoms) -CyH2y- unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms, - R5 has independently the same definitions as R4, or is alkylene of 3 to 18 linear carbon atoms; R | A is lower alkyl, - x is an integer from 3 to 5, - and is an integer from 1 to 6; Ra and Rb are each independently of the other, H, alkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, benzyl or phenyl, with the proviso that n in the groups - (Y?) N -Rj is 0 when R is H, - that no more than two Yj of the groups - (Y?) N- are O and n of the other group - (Y?) N- is 0, - and that n in the group - (Y7) n-is 0 when R3 is a direct bond, - and where also: X is -O- bivalent, -NH-, -S-, lower alkylene, or YjO is a direct bond u -0- (CH2) y- where y is an integer from 1 to 6, and whose terminal CH2 group is linked to the adjacent X in formula (Ib), - RJQ is H, alkyl 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, alkyl of the 12 carbon atoms -NH-, or -NRJARIB wherein R¡A is lower alkyl, and RjB is H or lower alkyl, - R 10j is lower alkyl, lower alkenyl, or aryl lower alkyl linear or branched; R102 independently of JOP has the same definitions as R * or? < or is aryl, or RjOi and 102 are together - (CH2) m-, where m is an integer from 2 to 6; R03 and Rj.04 are each independently of the other, linear or branched lower alkyl which may be substituted by alkoxy of 1 to 4 carbon atoms, or arylalkyl or lower alkenyl; or R103 and R104 are together - (CH2) Z-Ytl- (CH2) z- wherein Yp is a direct bond, -O-, -S- or -NR? B-, and R1B is H or lower alkyl, and each z independently of the other is an integer from 2 to 4.

6. A process according to any of claims 1 to 4, wherein an oligomer or polymer having one or more -OH and / or - groups is used as the macroinitiator. NH-, H-active, linked in a terminal or pendant manner, if desired by means of one or more bridging groups, the H atoms of whose H-active groups are partially or completely substituted by radicals Roo »wherein R2Q is a radical of the formula IVa OR IVb: -C (0) HN R4 NH (rv > l) O -C (O) NH - R 5 - NH - C - Y 10 X N R 103 R 1 O (IVb) where X, Y, Ylf Y2, Y10, R, R ,, R2, R3, R4, R5, R1 (?) RQI, 02 'R103 < R104 and n are as defined in claim 5.

7. A process according to any one of claims 1 to 4 or 6., wherein the oligomer or polymer is a natural or synthetic oligomer or polymer.

8. A process according to claim 7, wherein it is understood by a natural oligomer or polymer, a cyclodextrin, a starch, hyaluroacid, deacetylated hyaluroacid, chitosan, trehalose, cellobiose, maltotriose, maltohexaose, chytohexaose, agarose, chitin 50, amylose, a glucan, heparin, xylan, pectin, galactane, poly-galactosamine, a glycosaminoglycan, dextran, aminated dextran, cellulose, a hydroxyalkyl cellulose, a carboxyalkyl cellulose, fucoidan, chondroitin sulfate, a sulfated polysaccharide, a mucopolysaccharide, gelatin, zein, collagen, albumin, globulin, bilirubin, ovalbumin, keratin, fibronectin or vitronectin, pepsin, trypsin, or lysozyme, - and by an oligomer or synthetic polymer, a polymer,or a hydrolyzed polymer of one or more vinyl esters or ethers (polyvinyl alcohol); a polydiolefin or a hydroxylated polydiolefin, for example polybutadiene, polyisoprene, or chloroprene; polyacrylic acid or polymethacrylic acid, or a polyacrylate, polymethacrylate, polyacrylamide, or polymethacrylamide, if desired to have hydroxyalkyl or aminoalkyl radicals in the ester group or in the amide group, - a polysiloxane, if desired to have hydroxyalkyl or aminoalkyl groups; a polyether of one or more epoxides or glycidyl compounds and diols; a polyvinylphenol or a copolymer of vinylphenol and one or more olefinic comonomers; or a copolymer of at least one monomer from the group of vinyl alcohol, vinyl pyrrolidone, acrylic acid, methacrylic acid, or an acrylate containing hydroxyalkyl or aminoalkyl, methacrylate, or acrylic amide or methacrylic amide, or a hydroxylated diolefin or diolefin with one or more ethylenically unsaturated comonomers, for example acrylonitrile, an olefin, a diolefin, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, styrene, α-methylstyrene, a vinyl ether or a vinyl ester; or a polyoxaalkylene, if desired to have terminal OH or aminoalkyloxy groups.

9. A process according to any of claims 1, 2, 3, or 4, wherein the photoinitiator used is selected from: ilo (CH2) 2-0-pC6H4-C (0) -C (CH3) 2-N-morpholinyl

10. A process according to claim 1, wherein the surface in question is the surface of a contact lens or of an ophthalmic molded article.

11. A coated base material obtainable according to the process of any of the claims 1 to 9. A coated film obtainable according to the process of any of claims 1 to 9. 13. A coated contact lens obtainable according to the process of any one of claims 1 to 10. A modified base material obtainable according to the process of claim 2, omitting steps (c) and (d) described therein. 15. A modified base material that can be obtained by the process of claim 4, omitting the steps (e) and (f) described therein. 16. A modified base material according to claim 14 or claim 15, which is a film. 17. A modified base material according to claim 14 or claim 15, which is a contact lens. 18. A film comprising-, (a) a base material, and (b) a thin covalently bound layer on the surface, which consists of: (bl) constituents which are derived from at least one photoinitiator of the formula Ia or Ib, and (b2) a polymer of an olefin which is binds covalently with the isocyanate groups of the constituent (bl) by means of the groups which are co-reactive with the isocyanate groups. 19. A contact lens comprising: (a) a transparent organic base material, and (b) a thin covalently bonded layer on the surface, which consists of: (bl) constituents that are derived a. starting from at least one photoinitiator of formula Ia or Ib, and (b2) a polymer of an olefin that is covalently linked to the isocyanate groups of the constituent (bl) by means of groups that are co-reactive with the isocyanate groups. 20. A film comprising: (a) a base material, and (b) a thin layer covalently bonded to the surface, which consists of: (b) constituents that are derived from at least one photoinitiator of the formula or Ib, and the constituents (b) still contain isocyanate groups in the free form. 21. A contact lens, which comprises: (a) a transparent organic base material, and (b) a covalently bonded thin layer on the surface, which consists of: (b) constituents that are derived from at least a photoinitiator of the formula Ia or Ib, and the constituents (b) still contain isocyanate groups in the free form.